Bleaching and washing agents with enzyme bleaching system

ABSTRACT

A bleaching detergent composition comprising an enzyme having amino alcohol oxidase activity, a substrate for said enzyme, and a bleach catalyst or activator, a method of bleaching fabric stains with an enzymatic bleaching system comprising an enzyme having amino alcohol oxidase activity and a substrate for said enzyme, and a method of reducing dye transfer in a wash liquor by providing the liquor with an effective amount of an enzymatic bleaching system comprising an enzyme having amino alcohol oxidase activity and a substrate for said enzyme.

BACKGROUND OF THE INVENTION

This invention relates to a bleach or detergent which, besides typicalingredients, contains a bleaching system of an amino alcohol oxidase orD-amino acid oxidase and a substrate for this oxidase.

Modern heavy-duty detergents and bleaching washing aids, so-calledbleaches, normally contain an oxygen-based oxidizing agent, moreparticularly a peracid, a peracid salt, hydrogen peroxide or a substancewhich yields hydrogen peroxide under aqueous in-use conditions. Sincethe bleaching effect of hydrogen peroxide on its own is often found tobe inadequate, bleaching systems of a per compound which yields hydrogenperoxide in water and a bleach activator which generates a peracid underperhydrolysis conditions are generally used. The most prominent exampleof such a bleaching system is the widely used combination of alkalimetal perborate and N,N,N′,N′-tetraacetyl ethylenediamine. There hasbeen no shortage of attempts to improve this bleaching system bymodification. For example, it is proposed in International patentapplication WO 89/09813 to use a peroxidase enzyme, i.e. an enzyme whichcatalyzes the reaction of hydrogen peroxide with organic or inorganicsubstances, as bleach activator.

Besides inorganic hydrogen peroxide precursors such as, for example,perborate, percarbonate, perphosphate and persilicate, it has alsooccasionally been proposed to use enzymatic systems which are capable ofproducing hydrogen peroxide from oxygen, for example from atmosphericoxygen. Enzymes such as these are normally referred to as oxidases andare classified according to their substrate. Oxidases are redox enzymeswith the classification EC 1 (classification of the Enzyme Commission)which are generally flavine-dependent and of which the oxidized form iscapable of oxidizing a substrate. The resulting reduced form of theenzyme is reoxidized by molecular oxygen in aqueous systems, hydrogenperoxide being formed as another product. Examples of such enzymes andtheir substrates which follow the name of the enzyme are phenol oxidase,amino acid oxidase, xanthine oxidase, urate oxidase, alcohol oxidase,cholesterol oxidase and glucose oxidase.

DE-OS 19 18 729 describes detergents which, besides surfactants, contain0.5% by weight to 10% by weight of glucose oxidase and 5% by weight to30% by weight of glucose or starch. In the latter case, 0.5% by weightto 10% by weight of amyloglucosidase is said to be additionally present.DE-OS 20 64 146 discloses detergents containing 1% by weight to 50% byweight of water-soluble surfactant and 0.01% by weight to 2% by weightof lipoxidase. Polyunsaturated fatty acids are preferably present assubstrates for the lipoxidase. DE-OS 25 57 623 describes detergentswhich, in addition to surfactants and builders, contain 0.3% by weightto 10% by weight of urate oxidase, galactose oxidase or C₁₋₃ alcoholoxidase and 3% by weight to 30% by weight of uric acid, galactose orC₁₋₃ alcohols and/or corresponding ketoalcohols. European patent EP 0072 098 relates to liquid bleaches containing a C₁₋₄ alcohol oxidase anda C₁₋₄ alcohol. In European patent application EP 0 603 931, it isproposed to stabilize the glucose oxidase/glucose system in liquiddetergents by the addition of Cu²⁺ and/or Ag⁺ ions and to enhance thebleaching effect of the enzymatically produced hydrogen peroxide by thepresence of bleaching catalysts, more particularly metal porphines,metal porphyrines, metal phthalocyanines and/or haemine. The sameobjective is also followed by International patent application WO95/07972 which describes bleaches containing an enzymatic system toproduce hydrogen peroxide and a bleach-catalyzing coordination complexof Mn or Fe. International patent application WO 94/25574 discloses anL-amino acid oxidase of a certain strain of the microorganismTrichoderma harzianum and detergents containing this oxidase.

DESCRIPTION OF THE INVENTION

The problem addressed by the present invention was to provide ableaching formulation with improved effectiveness of the enzymaticallyproduced hydrogen peroxide under washing conditions.

It has now surprisingly been found that the bleaching effect of hydrogenperoxide produced enzymatically in typical washing, bleaching andcleaning liquors can be significantly increased, even in the absence oftypical activators, if the hydrogen peroxide is produced in situ throughthe use of amino alcohol oxidase or D-amino acid oxidase.

Accordingly, the present invention relates to a bleach or detergentcontaining an enzymatic bleaching system which is capable of producinghydrogen peroxide under in-use conditions and, optionally, syntheticsurfactant, organic and/or inorganic builder and other typicalingredients of bleaches or detergents, characterized in that thebleaching system consists of an enzyme having amino alcohol oxidase orD-amino acid oxidase activity and of a substrate for this enzyme.

The present invention also relates to the use of a bleaching system ofan enzyme having amino alcohol oxidase or D-amino acid oxidase activityand of a substrate for this enzyme for bleaching fabric stains underwashing conditions.

The present invention also relates to the use of a system of an enzymehaving amino alcohol oxidase or D-amino acid oxidase activity and of asubstrate for this enzyme for reducing dye transfer from dyed fabrics toundyed or differently colored fabrics when they come into contact underwashing or rinsing conditions.

Amino alcohol oxidases catalyze the oxidation of primary alcoholfunctions of amino alcohols by oxygen to the corresponding acid functionwith formation of hydrogen peroxide. Where they are used, it isessential that an amino alcohol with a primary alcohol function bepresent as substrate for the amino alcohol oxidase. The preferred aminoalcohol oxidase for the purposes of the present invention is cholineoxidase (EC 1.1.3.17) which is used together with its substrate cholinepreferably present as halide. D-amino acid oxidases (EC 1.4.3.3)catalyze the reaction:

 D-amino acid+H₂O+O₂→alpha-ketoacid+NH₃+H₂O₂

According to the invention, preferred substrates for D-amino acidoxidases are—either individually or in the form of mixtures—glycine,D-alanine, D-arginine, D-asparagine, D-aspartic acid, D-cysteine,D-glutamine, D-glutamic acid, D-histidine, D-isoleucine, D-leucine,D-lysine, D-methionine, D-phenyl alanine, D-proline, D-serine,D-threonine, D-tryptophane, D-tyrosine and D-valine, which may be usedwithout enantiomers or in admixture with their L-enantiomers. Accordingto the invention, it is particularly preferred to use D-alanine.

The oxidases suitable for use in the bleaches/detergents according tothe invention are enzymes obtainable from microorganisms or organs ofhigher animals which have an optimum pH preferably in the almost neutralto mildly alkaline range of about pH 6 to pH 9.5. The activity ofenzymes is normally expressed in U/g, the unit 1 U corresponding to theactivity of that quantity of enzyme which reacts 1 μmole of itssubstrate in 1 minute at pH 7/25° C. 1 U thus corresponds to 1/60μcatal. Choline oxidase as produced, for example, by alcaligenes speciesor by Arthrobacter globiformis is preferably used as the amino alcoholoxidase. D-amino acid oxidase of standardized activity, obtained forexample from pig's kidneys, is commercially available and, like cholineoxidase, can be obtained for example from the Sigma company. The oxidaseis preferably used in the bleach/detergent according to the invention insuch quantities that the bleaching composition/detergent as a whole hasan oxidase activity of 30 U/g to 20,000 U/g and, more particularly, 60U/g to 15,000 U/g. Bleaching systems/detergents with oxidase activitiesin the ranges mentioned release hydrogen peroxide sufficiently quicklyfor standard European machine washing processes. The enzymes with aminoalcohol oxidase or D-amino acid oxidase activity used in accordance withthe invention have a far higher activity than glucose oxidase underwashing conditions.

The amount of substrate present for the oxidase in the bleach/detergentaccording to the invention is determined by the amount of hydrogenperoxide required to obtain the desired bleaching result. As a guide, itmay be said that, in enzyme/substrate systems which release 1 mole ofhydrogen peroxide for every mole of substrate reacted, the presence ofabout 0.05% by weight to 0.6% by weight of the substrate in the washingor bleaching liquor is generally sufficient to obtain a good bleachingresult.

In contrast to the finding reported in WO 89/09813 that hydrogenperoxide has an increased bleaching effect on soiled textiles in thepresence of enzymes which degrade this compound, applicants have foundthat the simultaneous presence of peroxidases or catalases and thebleaching system of an enzyme having oxidase activity and a substratefor this enzyme in the bleaches/detergents according to the invention isdetrimental to the bleaching effect of the enzymatically producedhydrogen peroxide. Accordingly, if—for example for reasons of cost—it isintended to use enzyme preparations which, besides oxidase, also containcatalase and/or peroxidase (often isolated together with the oxidasefrom the producing microorganism), an inhibitor for thesehydrogen-peroxide-destroying enzymes is preferably added to thebleach/detergent according to the invention. Hydroxylammonium salts inparticular, for example hydroxylammonium sulfate, have been found to beextremely effective in this connection.

In principle, a bleach/detergent according to the invention may beformulated as required, for example as an aqueous or non-aqueous liquidbleach/detergent, a more or less viscous, aqueous or non-aqueous paste,a granular powder or in stick form or bar form, known processes of therelevant prior art being suitable for the production of suchformulations. In one preferred embodiment, the bleach/detergent ispresent in the form of a free-flowing particulate product, for exampleas a powder, with a bulk density of 300 g/l to 1,200 g/l and, moreparticularly, in the range from 500 g/l to 900 g/l. In particulateproducts such as these, the oxidase is preferably adsorbed onto an inertsupport material, i.e. onto a support material which is not a substratefor the enzyme, encapsulated in shell-forming substances or used in theform of standard granules with inorganic and/or organic supportmaterials. Enzyme granules such as these can be produced by processesknown with other enzymes, as described for example in German patent 1617 232, in German Offenlegungsschrifts 20 32 766 or 40 41 752 or inEuropean patent applications EP 0 168 526, EP 0 170 360, EP 0 270 608 orEP 0 304 331. If other typical detergent enzymes, including inparticular proteases, lipases, cutinases, amylases, pullulanases,hemicellulases and cellulases, are to be used in addition to oxidase,they may be accommodated in separate particles or may be used togetherwith oxidase in the form of multi-enzyme granules as described, forexample, in German patent applications DE 44 22 433 or DE 44 22 609 orin International patent applications WO 90/09440 or WO 90/09428 and inthe prior-art literature cited therein.

With powder-form bleaches/detergents according to the invention and withnon-aqueous liquid or paste-form bleaches/detergents, the oxidasesubstrate is not normally decomposed to any significant extent by theamino alcohol oxidase and/or D-amino acid oxidase in storage. In liquidor paste-form bleaches/detergents containing water, the enzymaticdecomposition of the substrate in storage can become a problem, albeitone that can be solved by denying oxygen access to the bleach/detergentaccording to the invention. Accordingly, water-containing liquid orpaste-form bleaches/detergents according to the invention, i.e. thosecontaining more than about 3% by weight of water, are preferably storedin hermetically sealed packs from which they are only removed shortlybefore use. In the case of institutional machine washing processes, thiscan readily be done by the automatic dispensing of the detergentaccording to the invention from the transit container itself, asdescribed for example in European patent EP 0 295 525. Liquid topaste-form bleaches/detergents according to the invention for use indomestic washing machines are preferably made up in portioned form, forexample in bag form, the container material surrounding a detergentaccording to the invention, for example film-form polyvinyl alcohol,being selected so that it only dissolves under in-use conditions, i.e.in the washing machine itself during the washing process, and releasesthe detergent so that the bleaching system present in the detergent onlythen comes into contact with the oxygen present in the air and formshydrogen peroxide.

In another embodiment of the bleach/detergent according to the inventionsimilarly intended to increase stability in storage, the enzyme havingoxidase activity and/or the substrate for this enzyme is encapsulated ina substance which is impermeable to the enzyme and/or its substrate atroom temperature or in the absence of water, but which becomes permeableto the enzyme and/or its substrate under in-use conditions. Organicsubstances melting at temperatures above room temperature, moreparticularly at temperatures of 35° C. to 75° C., for example fattyalcohols, polyglycols, paraffin waxes or fatty acid esters, may be usedfor this purpose. Substances which do not melt under in-use conditions,but which are soluble or dispersible in water, for example fine-particlealkali metal alumosilicate, layer silicate, clay or bentonite, are alsosuitable.

The composition of the bleaches/detergents according to the inventionmay otherwise be selected virtually as required within the limits ofknown formulations. In particular, the bleaches/detergents according tothe invention may contain builders, surfactants, water-miscible organicsolvents, other enzymes, sequestering agents, electrolytes, pHregulators, additional peroxygen bleaching agents and other auxiliaries,such as optical brighteners, redeposition inhibitors, foam regulators,bleach activators, dyes and fragrances and, if desired, additional dyetransfer inhibitors.

In addition to the bleaching system according to the invention,conventional bleach activators, i.e. compounds which form optionallysubstituted perbenzoic acid and/or aliphatic peroxocarboxylic acidscontaining 1 to 10 and, more particularly, 2 to 4 carbon atoms underperhydrolysis conditions, may be used. Conventional bleach activatorswhich contain O- and/or N-acyl groups with the number of carbon atomsmentioned and/or optionally substituted benzoyl groups are suitable.Preferred bleach activators are polyacylated alkylene diamines, moreparticularly tetraacetyl ethylenediamine (TAED), acylated glycolurils,more particularly tetraacetyl glycoluril (TAGU), acylated triazinederivatives, more particularly1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenolsulfonates, more particularly nonanoyl or isononanoyloxybenzenesulfonate, acylated polyhydric alcohols, more particularly triacetin,ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran andacetylated sorbitol and mannitol, and acylated sugar derivatives, moreparticularly pentaacetyl glucose (PAG), pentaacetyl fructose,tetraacetyl xylose and octaacetyl lactose, and acetylated, optionallyN-alkylated glucamine and gluconolactone. The combinations ofconventional bleach activators known from German patent application DE44 43 177 may also be used. Bleach activators such as these are normallypresent in quantities of 1% by weight to 10% by weight and, moreparticularly, in quantities of 2% by weight to 5% by weight. In additionto or instead of the conventional bleach activators mentioned above, thesulfonimines and/or bleach-boosting transition metal salts or transitionmetal complexes known from European patents EP 0 446 982 and EP 0 453003 may be present as so-called bleach catalysts. Suitable transitionmetal compounds include, in particular, the manganese-, iron-, cobalt-,ruthenium- or molybdenum-salen complexes known from German patentapplication DE 195 29 905 and the N-analog compounds thereof known fromGerman patent application DE 196 20 267, the manganese-, iron-, cobalt-,ruthenium- or molybdenum-carbonyl complexes known from German patentapplication DE 195 36 082, the manganese, iron, cobalt, ruthenium,molybdenum, titanium, vanadium and copper complexes withnitrogen-containing tripod ligands described in German patentapplication DE 196 05 688, the cobalt-, iron-, copper- andruthenium-ammine complexes known from German patent application DE 19620 411, the manganese, copper and cobalt complexes described in Germanpatent application DE 44 16 438, the cobalt complexes described inEuropean patent application EP 0 272 030, the manganese complexes knownfrom European patent application EP 0 693 550, the manganese, iron,cobalt and copper complexes known from European patent 0 392 592 and/orthe manganese complexes described in European patent EP 0 443 651 or inEuropean patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271,EP 0 549 272, EP 0 544 490 and EP 0 544 519. Combinations of bleachactivators and transition metal bleach catalysts are known, for example,from German patent application DE 196 13 103 and International patentapplication WO 95/27775. Bleach-boosting transition metal complexes,more particularly with the central atoms Mn, Fe, Co, Cu, Mo, V, Tiand/or Ru, are used in typical quantities, preferably in a quantity ofup to 1% by weight, more preferably in a quantity of 0.0025% by weightto 0.25% by weight and most preferably in a quantity of 0.01% by weightto 0.1% by weight, based on the bleach/detergent as a whole.

The bleaches/detergents according to the invention may contain one ormore surfactants, more particularly anionic surfactants, nonionicsurfactants and mixtures thereof. Suitable nonionic surfactants are, inparticular, alkyl glycosides and ethoxylation and/or propoxylationproducts of alkyl glycosides or linear or branched alcohols containing12 to 18 carbon atoms in the alkyl moiety and 3 to 20 and preferably 4to 10 alkyl ether groups. Corresponding ethoxylation and/orpropoxylation products of N-alkylamines, vicinal diols, fatty acidesters and fatty acid amides, which correspond to the long-chain alcoholderivatives mentioned in regard to the alkyl moiety, and of alkylphenols containing 5 to 12 carbon atoms in the alkyl group are alsosuitable.

Suitable anionic surfactants are, in particular, soaps and anionicsurfactants containing sulfate or sulfonate groupswith—preferably—alkali metal ions as cations. Preferred soaps are thealkali metal salts of saturated or unsaturated fatty acids containing 12to 18 carbon atoms. Fatty acids such as these need not even becompletely neutralized. Suitable surfactants of the sulfate type includethe salts of sulfuric acid semiesters of fatty alcohols containing 12 to18 carbon atoms and the sulfation products of the above-mentionednonionic surfactants with low degrees of ethoxylation. Suitablesurfactants of the sulfonate type include linear alkyl benzenesulfonatescontaining 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonatescontaining 12 to 18 carbon atoms and olefin sulfonates containing 12 to18 carbon atoms, which are formed in the reaction of correspondingmonoolefins with sulfur trioxide, and also α-sulfofatty acid esterswhich are formed in the sulfonation of fatty acid methyl or ethylesters.

Surfactants such as these are present in the detergents according to theinvention in quantities of, preferably, 5% by weight to 50% by weightand, more preferably, 8% by weight to 30% by weight while the bleachesaccording to the invention may even be surfactant-free and preferablycontain 0.1% by weight to 20% by weight and, more preferably, 0.2% byweight to 5% by weight of surfactants.

A bleach/detergent according to the invention preferably contains atleast one water-soluble and/or water-insoluble, organic and/or inorganicbuilder. Suitable water-soluble organic builders are aminopolycarboxylicacids, more particularly nitrilotriacetic acid and ethylenediaminetetraacetic acid, polyphosphonic acids, more particularlyamino-tris-(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethane-1,1 -diphosphonicacid, polycarboxylic acids, more particularly citric acid and sugaracids, and polymeric (poly)carboxylic acids, more particularly thepolycarboxylates of International patent application WO 93/16110obtainable by oxidation of polysaccharides, polymeric acrylic acids,methacrylic acids, maleic acids and copolymers thereof which may alsocontain small amounts of polymerizable substances with no carboxylicacid functionality in copolymerized form. The relative molecular weightof the homopolymers of unsaturated carboxylic acids is generally between5,000 and 200,000 while the relative molecular weight of the copolymersis between 2,000 and 200,000 and preferably between 50,000 and 120,000,based on free acid. A particularly preferred acrylic acid/maleic acidcopolymer has a relative molecular weight of 50,000 to 100,000.Suitable, albeit less preferred, compounds of this class are copolymersof acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl ester, ethylene, propylene and styrene, in whichthe acid makes up at least 50% by weight. Other suitable water-solubleorganic builders are terpolymers which contain two unsaturated acidsand/or salts thereof as monomers and vinyl alcohol and/or a vinylalcohol derivative or a carbohydrate as the third monomer. The firstacidic monomer or its salt is derived from a monoethylenicallyunsaturated C₃₋₈ carboxylic acid and preferably from a C₃₋₄monocarboboxylic acid, more particularly (meth)acrylic acid. The secondacidic monomer or its salt may be a derivative of a C₄₋₈ dicarboxylicacid, maleic acid being particularly preferred. In this case, the thirdmonomeric unit is formed by vinyl alcohol and/or preferably by anesterified vinyl alcohol. Vinyl alcohol derivatives in the form of anester of short-chain carboxylic acids, for example C₁₋₄ carboxylicacids, with vinyl alcohol are particularly preferred. Preferredterpolymers contain 60% by weight to 95% by weight, more particularly70% by weight to 90% by weight, of (meth)acrylic acid or (meth)acrylate,more preferably acrylic acid or acrylate, and maleic acid or maleate and5% by weight to 40% by weight and preferably 10% by weight to 30% byweight of vinyl alcohol and/or vinyl acetate. Most particularlypreferred terpolymers are those in which the ratio by weight of(meth)acrylic acid or (meth)acrylate to maleic acid or maleate isbetween 1:1 and 4:1, preferably between 2:1 and 3:1 and more preferablybetween 2:1 and 2.5:1. Both the quantities and the ratios by weight arebased on the acids. The second acidic monomer or its salt may even be aderivative of an allyl sulfonic acid substituted in the 2-position by analkyl group, preferably by a C₁₋₄ alkyl group, or by an aromatic radicalpreferably derived from benzene or benzene derivatives. Preferredterpolymers contain 40% by weight to 60% by weight and, moreparticularly, 45% by weight to 55% by weight of (meth)acrylic acid or(meth)acrylate, more especially acrylic acid or acrylate, 10% by weightto 30% by weight and preferably 15% by weight to 25% by weight ofmethallyl sulfonic acid or methallyl sulfonate and, as the thirdmonomer, 15% by weight to 40% by weight and preferably 20% by weight to40% by weight of a carbohydrate. This carbohydrate may be, for example,a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharidesbeing preferred. Sucrose is particularly preferred. Predetermined “weakspots” responsible for the ready biodegradability of the polymer arepresumably incorporated therein through the use of the third monomer.These terpolymers may be produced in particular by the processesdescribed in German patent DE 42 21 381 and in German patent applicationDE 43 00 772 and have a relative molecular weight of generally from1,000 to 200,000, preferably from 200 to 50,000 and more preferably from3,000 to 10,000. Other preferred copolymers are those described inGerman patent applications DE 43 03 320 and DE 44 17 734 whichpreferably contain acrolein and acrylic acid/acrylic acid salts or vinylacetate as monomers. The organic builders may be used in the form ofaqueous solutions, preferably in the form of 30 to 50% by weight aqueoussolutions, more particularly for the production of liquid formulations.All the acids mentioned are generally used in the form of theirwater-soluble salts, more particularly their alkali metal salts.

If desired, the organic builders may be present in bleaches/detergentsaccording to the invention in quantities of up to 40% by weight,preferably in quantities of up to 25% by weight and more preferably inquantities of 1% by weight to 8% by weight. Quantities near the upperlimit mentioned are preferably used in paste-form or liquid, moreparticularly water-containing, bleaches/detergents according to theinvention.

Suitable water-soluble inorganic builders are, in particular,polyphosphates, preferably sodium triphosphate. The water-insoluble,water-dispersible inorganic builders used are, in particular,crystalline or amorphous alkali metal alumosilicates which are employedin quantities of up to 50% by weight, preferably in quantities of notmore than 40% by weight and, in liquid bleaches/detergents, inquantities of 1% by weight to 5% by weight. Of these, crystalline sodiumalumosilicates of detergent quality, more particularly zeolite A, P andoptionally X, are preferred. Quantities near the upper limit mentionedare preferably used in solid particulate bleaches/detergents. Suitablealumosilicates have no particles larger than 30 μm in size, at least 80%by weight preferably consisting of particles less than 10 μm in size.Their calcium binding capacity, which may be determined in accordancewith German patent DE 24 12 837, is generally in the range from 100 to200 mg CaO per gram.

Suitable substitutes or partial substitutes for the alumosilicatementioned are crystalline alkali metal silicates which may be presenteither individually or in admixture with amorphous silicates. The alkalimetal silicates suitable for use as builders in the bleaches/detergentsaccording to the invention preferably have a molar ratio of alkali metaloxide to SiO₂ of less than 0.95:1 and, more particularly, in the rangefrom 1:1.1 to 1:12 and may be amorphous or crystalline. Preferred alkalimetal silicates are sodium silicates, more particularly amorphous sodiumsilicates with a molar Na₂O:SiO₂ ratio of 1:2 to 1:2.8. Amorphous alkalimetal silicates such as these are commercially available, for exampleunder the name of Portil®. Those with a molar Na₂O:SiO₂ ratio of 1:1.9to 1:2.8 may be produced by the process according to European patentapplication EP 0 425 427. They are preferably added in solid form andnot in the form of a solution in the production of thebleaches/detergents according to the invention. Preferred crystallinesilicates, which may be present either individually or in admixture withamorphous silicates, are crystalline layer silicates with the generalformula Na₂Si_(x)O_(2x+1).yH₂O, where x—the so-called modulus—is anumber of 1.9 to 4 and y is a number of 0 to 20, preferred values for xbeing 2, 3 or 4. Crystalline layer silicates which correspond to thisgeneral formula are described, for example, in European patentapplication EP 0 164 514. Preferred crystalline layer silicates arethose in which x in the general formula mentioned assumes the value 2 or3. Both β- and δ-sodium disilicates (Na₂Si₂O₅.yH₂O) are particularlypreferred, β-sodium disilicate being obtainable for example by theprocess described in International patent application WO 91/08171.δ-Sodium silicates with a modulus of 1.9 to 3.2 may be produced inaccordance with Japanese patent applications JP 04/238 809 and JP 04/260610. Substantially water-free crystalline alkali metalsilicates—produced from amorphous alkali metal silicates—with theabove-mentioned general formula, in which x is a number of 1.9 to 2.1,obtainable as described in European patent applications EP 0 548 599, EP0 502 325 and EP 0 452 428, may be used in the bleaches/detergentsaccording to the invention. Another preferred embodiment of thebleaches/detergents according to the invention uses a crystalline sodiumlayer silicate with a modulus of 2 to 3 obtainable from sand and soda bythe process according to European patent application EP 0 436 835. Thecrystalline sodium silicates with a modulus of 1.9 to 3.5 obtainable bythe processes according to European patents EP 0 164 552 and/or EP 0 293753 are used in another preferred embodiment of the bleaches/detergentsaccording to the invention. If alkali metal alumosilicate, moreparticularly zeolite, is also present as an additional builder, theratio by weight of alumosilicate to silicate, based on water-free activesubstances, is preferably 4:1 to 10:1. In bleaches/detergents containingboth amorphous and crystalline alkali metal silicates, the ratio byweight of amorphous alkali metal silicate to crystalline alkali metalsilicate is preferably 1:2 to 2:1 and, more particularly, 1:1 to 2:1.

Builders are present in the detergents according to the invention inquantities of up to 60% by weight and more particularly in quantities of5% by weight to 40% by weight whereas the bleaches according to theinvention are preferably free from the builders which merely complex thecomponents of water hardness and preferably contain not more than 20% byweight and, more particularly, from 0.1% by weight to 5% by weight ofheavy-metal-complexing agents, preferably from the group consisting ofamino-polycarboxylic acids, aminopolyphosphonic acids andhydroxypolyphosphonic acids and water-soluble salts and mixturesthereof.

Enzymes which may be used in addition to the enzymatic bleaching systemin the detergents according to the invention are enzymes from the classof proteases, lipases, cutinases, amylases, pullulanases and cellulasesand mixtures thereof. Enzymes obtained from fungi or bacteria, such asBacillus subtilis, Bacillus licheniformis, Streptomyces griseus,Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes orPseudomonas cepacia are particularly suitable. The enzymes optionallyused and the oxidase to be used in accordance with the invention may beadsorbed onto supports and/or encapsulated in shell-forming materials toprotect them against premature inactivation, as described for example inInternational patent applications WO 92/11347 or WO 94/23005. Theadditional enzymes mentioned are preferably present in thebleaches/detergents according to the invention in quantities of up to 5%by weight and more particularly in quantities of 0.2% by weight to 2% byweight.

The organic solvents suitable for use in the bleaches/detergentsaccording to the invention, particularly where they are present inliquid or paste-like form, include alcohols containing 1 to 4 carbonatoms, more particularly methanol, ethanol, isopropanol andtert.butanol, diols containing 2 to 4 carbon atoms, more particularlyethylene glycol and propylene glycol, and mixtures thereof and theethers derivable from the classes of compounds mentioned. Water-misciblesolvents of the type in question are present in the bleaches/detergentsaccording to the invention in quantities of preferably not more than 30%by weight and, more particularly, in quantities of 6% by weight to 20%by weight.

To establish a required pH value which is not automatically establishedby the mixture of other components, the bleaches/detergents according tothe invention may contain system-compatible and ecologically safe acids,more particularly citric acid, acetic acid, tartaric acid, malic acid,lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipicacid, and also mineral acids, more particularly sulfuric acid, or bases,more particularly ammonium or alkali metal hydroxides. pH regulatorssuch as these are present in the bleaches/detergents according to theinvention in quantities of preferably not more than 20% by weight and,more particularly, in quantities of 1.2% by weight to 17% by weight.

The production of the solid bleaches/detergents according to theinvention does not involve any difficulties and, in principle, may becarried out in known manner, for example by spray drying or granulation,the enzymatic bleaching system and any other heat-sensitive substancesbeing added at a later stage. To produce bleaches/detergents accordingto the invention with a high bulk density, more particularly in therange from 650 g/l to 950 g/l, it is preferred to apply a processcomprising an extrusion step as known from European patent EP 486 592.Detergents or bleaches according to the invention in the form of aqueoussolutions or other solutions containing typical solvents are producedwith particular advantage by simple mixing of the ingredients which maybe introduced into an automatic mixer either as such or in the form of asolution.

EXAMPLES

The formation of hydrogen peroxide with the aid of various oxidases wasinvestigated in a buffer system (Davies buffer) and in the presence ofan enzyme-, bleach- and bleach-activator-free detergent (concentration 5g/l) at pH 10/30° C. The H₂O₂ concentration was determinedphotometrically using the Lambert-Beer law via the peroxidase-catalyzedformation of a dye from 4-aminophenazone and chromotropic acid. Theconcentration of the particular oxidase substrate (D-alanine, cholinechloride or glucose) was 25 mmole/l. The oxidases were used inactivities of 1 U/ml. In the tests with D-amino acid oxidase and in thecomparative tests with glucose oxidase, hydroxylammonium sulfate wasadditionally present (concentration 1 mmole/l). The hydrogen peroxideconcentrations obtained after 30 minutes and 45 minutes are shown inTable 1 below.

TABLE 1 Hydrogen peroxide concentration [mmole/l] Buffer pH 10Detergent, pH 10 Enzyme 30 mins. 45 mins. 30 mins. 45 mins. D-amino acidoxidase^(a)) 0.6 0.9 1.9 1.9 Choline oxidase^(b)) 0.5 0.7 4.0 6.5Glucose oxidase^(c)) 0.06 0.1 0.3 0.3 ^(a))from pig's kidneys ^(b))fromalcaligenes ^(c))from Aspergillus niger

Under the typical in-use conditions for detergents, only a slightevolution of hydrogen peroxide could be measured where theglucose-oxidase/glucose system was used as opposed to the systemsaccording to the invention.

What is claimed is:
 1. A bleaching detergent composition comprising: a)an enzymatic bleaching system that produces hydrogen peroxide underaqueous conditions comprising an enzyme having amino alcohol oxidaseactivity and a substrate for said enzyme; b) a bleach activator; and c)a linear alkyl benzene sulfonate surfactant.
 2. A composition accordingto claim 1, wherein the enzymatic bleaching system comprises cholineoxidase and choline.
 3. A composition according to claim 2 having anoxidase activity of 30 U/g to 20,000 U/g.
 4. A composition according toclaim 3, said composition being in free-flowing particle form and havinga bulk density of 300 g/l to 1200 g/l.
 5. A composition according toclaim 4 having a bulk density of 500 g/l to 900 g/l.
 6. A compositionaccording to claim 2 having a liquid or paste form.
 7. A compositionaccording to claim 6 having a non-aqueous liquid or paste form.
 8. Acomposition according to claim 6 in the form of an aqueous liquid orpaste in a hermetically sealed container.
 9. A composition according toclaim 1, wherein the enzyme or the substrate are encapsulated in asubstance that is impermeable to the enzyme or substrate at roomtemperature.
 10. A method of bleaching fabric stains comprisingcontacting a fabric in need thereof with an effective amount of anenzymatic bleaching system comprising an enzyme having amino alcoholoxidase activity and a substrate for said enzyme in the presence of alinear alkyl benzene sulfonate surfactant.
 11. A method of reducing dyetransfer in a wash liquor from a dyed fabric to an undyed or differentlycolored fabric comprising providing said wash liquor with an effectiveamount of an enzyme having amino alcohol oxidase activity and asubstrate for said enzyme in the presence of a linear alkyl benzenesulfonate surfactant.